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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

A Step toward Process Electrification: Microwave-Assisted Co-Gasification of Waste Plastics and Biomass to Produce Clean Energy

Barely 9% of the 353 million metric tons of plastic waste produced worldwide over the last two decades has been recycled, with the majority of it being either landfilled or incinerated. Recycling and upcycling plastic waste is thus essential in mitigating environmental pollution. Gasification is the thermochemical conversion of solid carbon feedstock at high temperatures using a gasifying agent to produce hydrogen-rich syngas. Existing gasification technologies are energy-intensive and require high operating temperatures (>1000 °C), leaving them uncommercial. Microwave heating has sparked attention in a variety of chemical processes due to its specific advantages over traditional heating technologies, such as rapid and selective heating to improve process efficiency. NETL’s research team recently investigated the synergistic advantages of corn stover and mixed plastics in producing hydrogen-rich syngas via microwave heating. As a continuation of the research, this study provides an outlook over the non-catalytic versus catalytic effects of plastic-corn stover gasification via process electrification to enhance H2 production, minimize undesired tar, and improve process efficiency. Our aim is to provide complete electrification of the existing gasification process by using waste plastics as a starting block to produce valuable fuel and support the nation’s net zero goals.

Abedin, Ashraf↗
DOE OSTI2024

Microwave-Assisted Syngas Cleanup: Catalytic Reforming of Gasifier Tar Using a Low-Cost Iron Catalyst

The microwave-assisted gasification of plastic wastes to produce hydrogen-rich syngas is an attractive energy-saving plastic upcycling route, and the addition of biomass could improve the quality of the syngas produced; however, it could also increase the tar yield, which is an undesired, secondary product in this process. The presence of tars could result in downstream lines blockage, reactor down time and costly maintenance. Therefore, reducing or removing tar is desired. Due to its chemical complexity, toluene, which is one of the main tar constituents, could be used as a model tar compound. In this work, the microwave-assisted catalytic dry reforming of toluene was studied using Fe/Al2O3 as a catalyst, under CO2 at different reaction temperatures. The toluene reforming reaction was conducted using microwave and conventional thermal reactors. The results showed that under microwave irradiation, higher CO2 and toluene conversions, as well as better hydrogen yield can be observed compared to conventional toluene reforming at the same reaction temperature. The catalyst stability test was also investigated. Three reaction pathways were observed during microwave reaction.

Bai, Xinwei↗
DOE OSTI2026

Simultaneous Determination of Halogens and Metals in Waste Plastic Pyrolysis Oil by Inductively Coupled Plasma Mass Spectrometry

A major barrier to integrating pyrolysis-derived oil into conventional refinery technology is the presence of impurities, particularly halogens and metals, that can deactivate catalysts. This study presents a novel, cost-effective approach for the simultaneous analysis of a subset of halogens, metals, nonmetals, and metalloids in complex, industrially relevant distilled pyrolysis oil samples, this was previously achievable only through multiple techniques. Excellent results were obtained using a widely accessible inductively coupled plasma mass spectrometry (ICP-MS) method with helium gas mode and standard laboratory consumables, enabling high-throughput analysis and efficient evaluation of adsorbent performance. Sample preparation is straightforward, requiring only dilution in a compatible matrix, and provides accurate and precise quantification, with 75%–137% spike recovery for Be, Ti, V, Cr, Fe, Ni, Co, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, and 62%–65% spike recovery for Cl and 109%–133% spike recovery for Br. Additionally, an enhanced version of the method using ICP-MS/MS and hydrogen gas is described, which has higher accuracy with 69%–112% spike recovery for Be, B, Ti, V, Fe, Co, Ni, Cu, As, Se, Mo, Cd, Sb, Tl, and Pb, with 85%–102% spike recovery for Cl and 63%–93% spike recovery for Br. Helium mode detection limits for industrially relevant elements (V, Fe, Ni, Cu, As, and Pb) are less than 1.7 µg/kg, and less than 0.2 mg/kg for Br and Cl. Furthermore, this methodology facilitates rapid systematic evaluation of adsorption capacities of materials under time-on-stream conditions and supports robust comparisons across diverse operating environments.

Lazarcik, James [University of Wisconsin-Madison, ↗
DOE OSTI2022

Role of Bifunctional Ru/Acid Catalysts in the Selective Hydrocracking of Polyethylene and Polypropylene Waste to Liquid Hydrocarbons

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste to liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal C–C bond scission. In this study, a variety of catalysts were investigated for the reductive deconstruction of polyethylene (PE) and polypropylene (PP) to identify supports that promote nonterminal C–C bond scission. We found that Ru nanoparticles supported on Brønsted-acidic zeolites with the faujasite (FAU) and Beta (BEA) topologies were highly active for the cleavage of C–C bonds in PE and PP, exhibiting improved liquid yields and suppressed methane formation. For the deconstruction of PE, supporting ruthenium nanoparticles (5 wt %) on FAU increased the yields of liquid alkanes to 67% compared to 33% over an inert silica support (5 wt % Ru/SiO 2 ) at 200 °C, 16 h, under 30 bar of H2. A dramatic selectivity enhancement toward liquid hydrocarbons was also observed for PP over Ru/FAU and Ru/BEA compared to Ru/SiO 2 . To understand the origin of this selectivity improvement, a combination of ex situ and operando characterization techniques were used to reveal that both catalyst structure and acidity play key roles in PE and PP conversion. Operando X-ray absorption spectroscopy studies with model polyolefins over Ru-supported catalysts with varying acidity levels revealed that the local chemical environment of Ru [0] during the reaction is consistent across multiple acidic supports, although the onset of reduction during synthesis of the nanoparticles varies across different supports. These results, combined with reactivity data, demonstrate the importance of the acid-noble metal cooperativity in promoting selective C–C bond scission toward liquid alkanes that shifts the mechanism from hydrogenolysis to ideal hydrocracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗
DOE OSTI2020

Direct Recycling of Spent NCM Cathodes through Ionothermal Lithiation

Ionic liquids (ILs) are a family of nonconventional molten salts that offer many advantages, such as negligible vapor pressures, negligible flammability, wide liquidus ranges, good thermal stability, and much synthesis flexibility. The unique solvation environment of these ILs provides new reaction or flux media for controlling formation of solid-state materials with a minimum perturbation of morphologies. A successful lithiation via ionothermal synthesis using a cost-effective Li halide as Li source and recyclable ILs as solvents is reported in this study for the direct recycling of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM 111) cathodes. In addition, the ionic liquids can be readily recycled and reused after ionothermal lithiation. The lithiation of spent cathodes can enable the direct recycling of spent cathode materials in lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Zeolite‐Based Catalysts for Conversion of Oxygenated Polymer Waste by Positron Annihilation

Positron Annihilation Lifetime Spectroscopy (PALS) has been employed to investigate the catalysts HZSM-5 and MESO−Y, which play a pivotal role in catalyzing and upgrading plastics, with a primary focus on oxygenated polymers, thereby transforming existing plastic materials into simpler, higher-quality value-added products. Here, in this study, PALS was systematically compared with other complementary analytical techniques. The research outcomes have successfully demonstrated the efficacy of PALS in elucidating the morphology and topology of zeolites at micro/meso-meter scales. The first experiment focuses on H-ZSM-5 zeolite subjected to treatments involving polyurethane and polypropylene. The second experiment delves into H-ZSM-5 zeolites with varying Si/Al ratios, both before and after conversion. The third experiment investigates Y zeolites that are surfactant templated to induce meso-porosity, examining their fresh state as well as their post-conversion condition. The PALS analysis was supplemented by BET (Brunauer-Emmett-Teller) analysis and NMR (Nuclear Magnetic Resonance) spectroscopies. Notably, PALS exhibits superior sensitivity, at the sub-nanometer scale, suggesting its potential as a preferred complementary method for catalysis studies. In conclusion, the integration of PALS into the repertoire of analytical tools enhances our understanding of catalyst behavior and catalytic processes, offering valuable insights for the advancement of plastic recycling and catalysis research.

32 - ENERGY CONSERVATION, CONSUMPTION, AND UTILIZA↗
DOE OSTI2026

Hydrotreatment of Nylon 66 and Amide Model Compounds Over Sulfided NiMo Catalysts

Molybdenum sulfide-based catalysts, such as nickel–molybdenum on alumina (NiMoS x /Al 2 O 3 ), are widely used in hydrotreating and have potential for catalyzing waste plastic conversion via hydrogenolysis, yet their performance, such as reaction kinetics and network, for amide-rich polymer feeds is poorly defined. Here we combine Nylon 66 with the amide model compound, N,N-dibutylhexanediamide (DBDAD), to quantify hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) chemistry in a stirred batch reactor (53 bar H 2 , 280–320°C). DBDAD conversion is near-linear with time, indicating strong adsorption of the substrates on the active sites. Time-resolved product identification indicates parallel C─O first-cleavagedeoxygenation (DO) and C─N first-cleavagedenitrogenation (DN) sequences proceeding through amine and diol intermediates, respectively, to C 4 ─C 6 alkanes. Increasing temperature shifts selectivity toward DN, decreasing the initial r(DO)/r(DN) from 1.38 (280°C) to 0.69 (320°C), with an apparent activation energy of 173 kJ mol −1 for DBDAD conversion. At 300°C, nylon 66 converts faster than DBDAD, producing a complex mixture of oxygen- and nitrogen-containing species and an initial rate ratio r(DO)/r(DN) of 1.6. No heteroaromatic nitrogen products are detected by the method used. These results provide reaction pathways and product signatures relevant to hydro-processing catalysts exposed to polyamide-derived streams.

Nylon 66↗
DOE OSTI2025

Chemically Recyclable Polyester Thermosets from Activated Adipic Acid and Renewable Polyols

This study outlines a method for producing chemically recyclable crosslinked polyesters using renewable polyols-glycerol and sorbitol-combined with adipic acid (AA), which is transformed/activated into a polyanhydride mixture prior to use. A three-step procedure has been designed: 1) an acid-catalyzed reaction of AA with nontoxic isopropenyl acetate or acetic anhydride to form a crosslinking mixture (CLM) made of adipic-acetic mixed polyanhydrides; 2) a solvent- and additive-free process where glycerol or sorbitol, or a combination thereof, is reacted with the CLM to achieve a prepolymer, and 3) a casting/molding of the liquid viscous prepolymer to yield a thermoset as the end product. Different thermosets (eight examples) are prepared by changing the reagents ratio. These solids are thoroughly characterized by tensile tests, DMA, high-resolution magic angle spinning and solid-state NMR, thermal gravimetric analysis, DSC, and fourier transformed infra red (FT-IR) spectroscopy. The formation of cross-linked polyesters is confirmed in all cases, but mechanical properties varied significantly from one specimen to another. Interestingly, a tensile strength up to 18 MPa-approximately an order of magnitude higher than similar polymers-is achieved when sorbitol and the CLM are used in a 1:1 wt% ratio. The chemical recycle of the resulting polymers is achieved via methanolysis with quantitative recovery of the monomeric units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polyolefin Innovations Toward Circularity and Sustainable Alternatives

The unprecedented growth and socioeconomic impacts of polyolefins clearly outline a major success story in the world of polymer science. Polyolefins revolutionizes industries such as health care, construction, and food packaging. Despite the benefits of polyolefins, there is a rising concern for the environment due to high production volume (i.e., fossil fuel consumption), often short usage time, and problems related to waste management and accumulation in the natural environment. Creating a circular economy for polyolefins through effective recycling technologies has the potential to decrease the environmental impact of these materials. This perspective discusses polyolefins and their impact, existing and emerging recycling/upcycling solutions, and recycle-by-design alternatives that are challenging the status quo.

circular economy↗
DOE OSTI2025

Oxidation of n-alkanes using TS-1 and H 2 O 2 : Effects of chain length and solvents

The selective oxidation of n-C 8 H 18 , n-C 12 H 26 , n-C 16 H 34 , n-C 20 H 42 , and n-C 36 H 74 was studied with a goal of using these as models to provide insight into how to functionalize polyolefins. Reactions were carried out using a TS-1 catalyst and H 2 O 2 in a batch reactor with different cosolvents, including methanol, acetone, acetonitrile, methyl ethyl ketone, and methyl butyl ketone. Rates decreased with increasing alkane size, possibly due to the reduced solubility of larger alkanes into the water-rich phases. Cosolvents that promote the partitioning of alkanes in the aqueous phase increased the rates. 1 H NMR spectroscopy demonstrated that ketones were the primary products, although some alcohols also formed. There was preferential reaction at the 2 position in the alkanes, but reaction at central carbons was also observed. The results of this study suggest strategies for using this catalytic chemistry to functionalize polyolefins.

Alkane oxidation↗
DOE OSTI2022

Hydrogenolysis of n -eicosane over Ru-based catalysts in a continuous flow reactor

The hydrogenolysis of n-eicosane (C 20 H 42 ) was studied under differential conditions over Ru-based catalysts including Ru/SiO 2 , Ru/TiO 2 , and Ru/SBA-15, using a continuous flow reactor that was specially designed for large hydrocarbon reactants that are solids at room temperature. Similar rates and product distributions were obtained for Ru/SiO 2 and Ru/SBA-15 at 433 K, with the most abundant products being C 1 and C 19 hydrocarbons and smaller amounts of C 8 to C 18 also being produced. The higher yield of C 1 and C 19 indicates that cleavage of the terminal C-C bond is somewhat more facile than an internal C-C bond. At 473 K the product distribution shifted to mostly C 1 suggesting that, at this temperature, the adsorbed alkyl fragments undergo complete C-C bond scission prior to desorbing. Here, the conversion was also found to be inversely proportional to the H 2 pressure. Similar results were obtained for Ru/TiO 2 except this catalyst was found to be less active than both Ru/SiO 2 and Ru/SBA-15.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mass transfer in catalytic depolymerization: External effectiveness factors and serendipitous processivity in stagnant and stirred melts

Several heterogeneous catalysts are being developed to recycle plastics. Most operate in viscous polymer melts, where external mass transfer effects could limit the supply of co-reactants to active sites. External mass transfer can also impede the diffusion of long chain products away from the catalyst after each cut. Product egress limitations could potentially confer unintentional processivity to catalyst operation, i.e. a tendency for the catalyst to repeatedly cut the same chain after an initial encounter. We formulate reaction–diffusion equations to quantify mass transfer effects on the co-reactant transport to the catalyst and the degree of serendipitous processivity. Results are developed for catalysts in stagnant or stirred melts, with simple expressions involving Damkohler, Peclet, and Sherwood numbers, i.e. dimensionless combinations of rate constants, catalyst particle size, polymer diffusivities, and shear rates (where applicable). In conclusion, we estimate the impact of these effects for a spherical core–shell catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Design principles for intrinsically circular polymers with tunable properties

This perspective discusses a set of design principles for next-generation kinetically trapped, intrinsically circular polymers (iCPs) that are inherently, selectively, and expediently depolymerizable to their monomer state once their kinetic barriers of deconstruction are overcome, thereby enabling not only the ideal shortest chemical circularity but also tunable performance properties. After describing four elements of the design principles - thermodynamics and kinetics, strategies to overcome trade-offs and unify conflicting properties, predictive modeling, and supply-chain life-cycle assessment and techno-economic analysis, which are illustrated with state-of-the-art examples - it concludes with presenting key challenges and opportunities for sustainable development of iCPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Microwave-assisted co-gasification of mixed plastics and corn stover: A synergistic approach to produce clean hydrogen

Co-gasification of waste plastic and corn stover into hydrogen is an effective way of reducing hydrogen cost and carbon footprint. However, current gasification technologies are energy intensive and cannot accommodate flexible feedstock. Microwave gasification offers several advantages including higher H 2 yield and enhanced selectivity to syngas over tars. Herein this work presents parametric optimization study of microwave co-gasification of mixed plastics and corn stover for hydrogen-rich syngas. High hydrogen yields of 30.5 mmol H2 /g feed at 700 °C were obtained using a microwave reactor, as opposed to 0.9 mmolH 2 /g feed at 700-950 °C with conventional heating. Hydrogen yields are >98% of the theoretical extractable hydrogen from feedstock. Microwaves enhanced plastic and corn stover synergy and reduced tar yields. H-poor carbon formation resulting from the dehydrogenation of tar and coke, and light olefins decomposition, triggered by the external microwave electric fields, allowed further cracking of intermediate hydrocarbons to produce additional H 2 .

30 DIRECT ENERGY CONVERSION↗